Improved catalytic process for producing baked alkyd resin enamel coating compositions cross-linked with etherified trimethylolated crotonylidenediurea or etherified methylolated 2,7-dioxo-4,5-dimethyl-decahydropyrimido-{8 4,5-d{9 -pyrimidine

ABSTRACT

Method for producing baked enamel coatings which comprises applying to a substrate an alkyd resin in the presence of an aminoplast and an amyl acid phosphate and heat curing the coating. Amyl acid phosphate, when employed as a catalyst for heat-curing alkyd resin coating compositions cross-linked with etherified trimethylolated crotonylidenediurea or etherified methylolated 2,7-dioxo-4,5-dimethyl-decahydropyrimido-(4,5-)pyrimidine, provides enamels of improved whiteness and color stability. The use of amyl acid phosphate in conjunction with urea as a catalyst system for heat-curing the aforementioned resins is also disclosed.

United States Patent 1191 1111 3,808,039 Kuzma Apr. 30, 1974 [54] IMPROVED CATALYTIC PROCESS FOR 3,016,555 1/1962 Penoyer 117 161 x PRODUCING BAKED ALKYD RESIN 3,063,870 11/1962 Wakeman et a1 117/161 X 3,160,618 12 1964 Delacretaz 117/161 x ENAMEL COATING COMPOSITIONS 3,231,374 1/1966 Sciambi 117 62.2 CROSS-LINKED WITH ETHERIFTED 3,654,193 4/1972 Seiner 117/161 x TRIMETHYLOLATED 3,309,327 3/1967 Gayer 260/850 CROTONYLIDENEDIUREA OR ETHERIFIED METHYLOLATED 2,7-DIOXO-4,5-DIMETHYL- DECAHYDROPYRIMIDO-[4,5-D]- PYRIMIDINE Inventor: Edward J. Kuzma, Woodbridge,

Assignee: Celanese Corporation, New York,

Filed: May 17, 1971 Appl. No.: 144,270

References Cited UNITED STATES PATENTS 9/1954 Ericks 117/161 X Primary Examiner-William D. Martin Assistant Examiner-Dennis C. Konopacki Attorney, Agent, or FirmThomas J. Morgan; Marvin Turken; John A. Shedden [5 7] ABSTRACT Method for producing baked enamel coatings which comprises applying to a substrate an alkyd resin in the presence of an aminoplast and an amyl acid phosphate and heat curing the coating. Amyl acid phosphate, when employed as a catalyst for heat-curing alkyd resin coating compositions cross-linked with etherified trimethylolated crotonylidenediurea or etherified methylolated 2,7-dioxo-4,5-dimethyldecahydropyrimido-[4,5-]-pyrimidine, provides enamels of improved whiteness and color stability. The use of amyl acid phosphate in conjunction with urea as a catalyst system for heat-curing the aforementioned resins is also disclosed.

5 Claims, No Drawings IMPROVED CATALYTIC PROCESS FOR PRODUCING BAKED ALKYD RESIN ENAMEL COATING COMPOSITIONS CROSS-LINKED WITH ETHERIFIED TRIMETHYLOLATED CROTONYLIDENEDIUREA OR ETHERIFIED METI-IYLOLATED 2,7-DIOXO-4,5-DIMETHYL- DECAI-IYDROPYRIMIDO-[3,S-D]-PYRIMIDINE BACKGROUND OF THE INVENTION This invention relates to the production of baked enamels. More particularly, it-relates to a catalyst system for curing alkyd enamel resins to produce coatings having a high degree of whiteness.

Alkyd resin enamels useful for coating kitchen appliances, washing machines, automobiles, and the like, must meet very rigorous specifications in view of their exposure to weather and various chemicals, including detergents, caustics, acids, alcohols, and staining agents. These enamels must also exhibit satisfactory gloss, hardness, impact resistance, curing rates, and the like. Furthermore, in addition to the aforementioned properties, an enamel for use in coating kitchen and laundry appliances (e.g., stoves, refrigerators, washing machines, and the like) must be capable of exhibiting good whiteness. While satisfactory whiteness is known to be attainable by the incorporation of appropriate whiteners into the coating formulation, it would be more desirable to achieve superior whiteness as an inherent property of the coating itself, rather than have to resort to the expedient of adding extraneous agents to achieve this goal.

A baked enamel presently enjoying substantial commercial success is prepared from alkyd resins containing aminoplasts of the urea-formaldehyde and melamine-formaldehyde type, including the butylated derivatives thereof..The alkyd resin components are generally oil-modified polyester reaction products of polybasic acids, e.g., a phthalic acid or its anhydride, and a polyol, e.g., a triol such as glycerol. Optionally, a minor proportion of a monobasic acid or a dibasic acid, such as benzoic acid, substituted benzoic acid, adipic acid, or thelike, can be present. 1

Of the condensation products of amines or amides, such as triazines, diazines, triazoles, guanidines, guanamines, and the like, with aldehydes, such as formaldehyde and acetaldehyde, the melamine-formaldehyde resins have, in general provided the most desirable overall enamel properties as aminoplast components of alkyd resins. Urea-formaldehyde resins have been quite successful, also, not so much because of their overall effectiveness, particularly when compared with mela- Another object is to provide a means for producing baked enamels having the cost advantages presently enjoyed by the urea/aldehyde-containingcoating resms.

Yet another object is to provide a means for producing baked enamels which is inherently capable of producing such coatings in a form having excellent whiteness.

These and other objects of the present invention, as well as a fuller understnading of the advantages thereof, can be had by reference to the following detailed description and claims.

SUMMARY OF THE INVENTION The above objects are achieved according to the present invention by the discovery that amyl acid phosphate, when used as the catalyst for the heat curing of specific and novel baking enamels, provides coatings which, in addition to meeting the usual requirements of resistance to weathering and various chemicals, satisfactory gloss, hardness, impact resistance, curing rates, and the like, also exhibit unusually good whiteness as compared to the whiteness of conventional resins cured with catalysts heretofore employed in the prior art. The term amyl acid phosphate refers to mono-amyl phosphate, di-amyl phosphate, and mixtures thereof, which are represented collectively by the following formula:

wherein R is a hydrogen substituent or an n-amyl sub stituent (i.e., -CH CI-I CH CI-I CI-I subject to the proviso that at least one of the R groups is an n-amyl substituent. Amyl acid phosphate is conveniently available from Hooker Chemical Corporation, Niagra Falls, New York. This material, which is a mixture of monoand di-amyl phosphate, is a colorless-to-light yellow liquid.

It is a feature of the present invention that amyl acid phosphate can be advantageously utilized as a catalyst for the heat-curing of certain novel alkyd coatings resins containing, as cross-linking agents, novel aminoplast compounds having either of the following general formulae:

0 II CHzOR ROH:CN O

' CHzOR A Etherified methylolated 2,7-di0xo4,S-dimethyl-decahy- ..drvisrri vt M r mi V wherein n is an integer from I to 4 and R is a hydrogen substituent or the alkyl residue of a monohydric alcohol, subject to the proviso that at least one of the R groups is said alkyl residue in each of formulae (C) and (B).

Compounds of formula (C) are disclosed in copending and commonly assigned US. application Ser. No. 135,749 filed Apr. 20, 1971 by Alan L. Peterkofsky, James E. Tracy, and Paul M. Schumacher and entitled Etherified Trimethylolated Crotonylidenediurea and its Use in Alkyd Resin Coating Compositions.

Compounds of formula (B) are disclosed in compending and commonly assigned U.S. application Ser. No. 135,747 filed Apr. 20, 1971 by James E. Tracy, Paul M. Schumacher, and Alan L. Peterkofsky and entitled Aminoplast Material and Use Thereof in Alkyd Resin Coating Compositions.

Compounds having the formula (B) and (C) constitute two novel classes of materials having unusual aminoplastic properties," so to speak, in enamels of the alkyd resin type, particularly with respect to hardness, chemical resistance, curing rates, and other like properties. Not only are these compounds generally superior to the urea-aldehyde aminoplasts but they are comparable and superior, in significant respects, to the relatively expensive melamine-aldehyde type resins.

Furthermore, by utilizing amyl acid phosphate as a catalyst in the curing of coating resins containing the aforementioned novel cross-linking agents, extraordinary whiteness is achieved. This feature of the present invention is especially advantageous in coating applications where whiteness is desired, e.g., in enamel coatings for kitchen and laundry applications.

In forming baked enamel coatings according to the process of the present invention, an alkyd resin coating composition is heat cured in admixture with a quantity of either or both of the aforementioned aminoplast compounds (B) and (C). The curing is faciliated by the incorporation into the reaction mixture of a catalytically effective amount of amyl acid phosphate (A). Desirably, the alkyd resin coating composition component is present in a concentration of between about 40 and about 95 percent by weight, based on the total weight of the alkyd resin and aminoplast. The aminoplast, accordingly, would be present in amounts of between about 5 and about 60 percenton the same weight basis. The catalyst amyl acid phosphate is desirably present in amounts of between about 0.05 and about 2 percent by weight, based on the total weight of the baked enamel coating composition. Quantities of catalyst less than about 0.05 percent tend to be ineffective, whereas amounts much in excess of 2 percent tend to discolor the final coating and diminish the hardness thereof. Preferably, the alkyd resin component is present in a concentration of between about 55 and about 93 percent by weight, while the amyl acid phosphate is preferably employed in amounts of between about 0.1 and about 1 percent by weight. Curing temperatures employed in the present process are generally those conventionally used in the baked enamel art. The choice of a particular temperature will usually be determined by such factors as desired curing rates, degree of cure (cross-linking), and the like. Generally, such curing temperatures will lie somewhere between about 200 F. and about 400 F., and preferably between about 250 F. and about 300 F.

In a preferred mode according to the present invention one part by weight of a 20 percent by weight solution of amyl acid phosphate in methanol is added to 100 parts by weight of an alkyd resin/aminoplast paint formulation. The paint is then sprayed on the surface to be coated, air dried for 10 to 15 minutes, and finally baked at elevated temperature. It is a further feature of the present invention that, when a small quantity urea say, about five parts of 10 weight percent methanolic urea are added to the above paint formulation, increased hardness and extremely white coatings are obtained. For some unknown reason, the incorporation of urea in amounts greater than that mentioned above (i.e., about 0.5 percent by weight of the enamel coating composition), does not enhance the hardness or whiteness beyond that already indicated. Desirably urea in an amount of at least about 0.1 percent and preferably about 0.2 to about 0.7 percent by weight is employed.

DESCRlPTlON OF THE PREFERRED EMBODIMENTS The following examples are presented for the purpose of illustrating present invention. In the examples, parts and percentages are by weight unless otherwise indicated. It should be clearly understood that the examples give generally preferred embodiments which are not intended to unduly limit the scope of the present invention; in other words, it will be apparent to the person skilled in the art that numerous modifications, extensions and variations are clearly within the spirit and scope of the invention.

EXAMPLE 1 Preparation of Methylolated Crotonylidenediurea To a suitable reaction vessel equipped with conventional agitation means are charged 239 grams (2.94 moles) of 37 percent formalin (uninhibited) and 15 grams of a 10 percent aqueous solution of sodium carbonate. To the resulting mixture are added, with agitation, 172 grams (1.0 mole) of crystalline crotonylinediurea. The reaction mixture, which has a pH of between about 9 and about 9.5, is heated to reflex temperature over the course of about 20 minutes and maintained at the reflux temperature for about 5 minutes. The reaction mixture is then cooled to ambient temperature, the pH is adjusted to 7.0, and the reaction mixture filtered to remove insolubles. The clear filtrate contains 2.8 percent free formaldehyde as determined by the sodium sulfite method described in Walker, Formaldehyde, 3d ed, p. 486 (Reinhold, NY. 1964). The concentration of aminoplast material in the aqueous filtrate is 60 percent by weight as determined gravimetrically, i.e., by evaporating an aliquot sample of the solution at C for 6 hours and weighing the residue. The aminoplast is methylolated crotonylidenediurea (C).

EXAMPLE 11 This example illustrates a variant of the procedure used in Example 1 to produce the methylolated crotonylidenediurea:

To a suitable reaction vessel equipped with conventional agitation means are charged 4055 grams (50 moles) of 37 percent formalin (uninhibited") and grams of a 10 percent aqueous solution of sodium carbonate. To the resulting mixture is added, with agitation, 1720 grams (10 moles) of crystalline crotonylidenediurea. The reaction mixture having a pH of between about 9 and about 9.5, is then heated at reflux temperature for 5 minutes and cooled to ambient temperature. An additional charge of 150 grams of l0 percent aqueous sodium carbonate and 1,204 grams (7 moles) of crotonylidenediurea are added and the reaction mixture is again heated to reflux temperature and maintained thereat for 30 minutes. Upon re-cooling the reaction mixture to ambient temperature, neutralizing the pH, and filtering, a solution of methylolate crotonylidenediurea is obtained which contains 2.7 percent unreacted formaldehyde.

EXAMPLE 111 Preparation of Butoxymethylated Crotonylidenediurea The clear filtrate of Example 1 is charged to a reaction vessel equipped with a phase separation head, and the pH is adjusted to a value of 3.0 by the addition of 25 percent aqueous formic acid. An amount (370 parts) of butanol is added to the reaction vessel and the system is heated to reflux temperature (about 100 C) and azeotropic distillation of water from the reaction mixture is continued until the temperature of the resin system reaches 117 C. The system is then cooled to ambient temperature and the product, butylated methylolated crotonylidenediurea adjusted to a solids content of 50 percent.

EXAMPLE 1V Preparation of Cyclohexyloxymethylated Crotonylideneduirea The clear filtrate of Example 1, above, is charged to a reaction vessel equipped with a phase separation head, and the pH is adjusted to a value of 3.0 by the addition of 25 percent aqueous formic acid. An amount (5,000 grams; 50 moles) of cyclohexanol is added to the reaction vessel and the system heated to reflux temperature and azeotropic distillation of water from the reaction mixture is continued until the temperature reaches about 130 C. To guard against product resin decomposition or polymerization, azeotropic distillation during the final stages is carried out under vacuum. The system is then cooled to ambient temperature and the product, cyclohexylated trimethylol crotonylidenediurea, adjusted to the desired solids content.

EXAMPLE V Preparation of Methoxymethylated Crotonylidenediurea This example illustrates a variant of the procedure used in Examples 111 and 1V to produce an alkylated (i.e., methylated) methylolated crotonylidenediurea.

An amount (272.0 parts) of 55 percent methyl Formcel containing 149.6 parts of formaldehyde (55 percent by weight), 95.2 parts of methanol (35 percent by weight) and 10 percent water is charged to a reaction vessel, and the pH is adjusted to a value of 3.0 by the addition of sufficient 25 percent aqueous formic acid. To the reaction vessel is then added 172.0 parts of crotonylidenediurea. The system is heated to reflux temperature (about 96 C) and maintained thereat for approximately 1 hour. At the end of this period, the temperature of the reaction mixture is reduced to approximately 55 C, followed by the addition of 262.0 parts of methanol. This temperature is maintained for a period of about 2 hours, during which time the pH is kept constant at 3.0 by the addition of appropriate quantities of 25 percent formic acid. At the end of the 2-hour holding period, the reaction system is cooled to ambient temperature and the pH adjusted to 7.8 with 10 N sodium hydroxide. The reaction mixture is then filtered and evaporated under reduced pressure to remove excess methanol and water of reaction. The resulting residue of methylated trimethylol crotonylidenediurea is re-dissolved in sufficient isopropanol to produce a solution containing 50 percent solids.

EXAMPLE Vl Preparation of Butoxymethylated Crotonylidenediurea Butyl Formcel (2060 parts) containing 82.4 parts of formaldehyde (40 percent by weight) and 109.2 parts of butanol (53 percent by weight) and n-butanol (62.0 parts) are charged to a reaction vessel equipped with a phase separation head, and the pH is adjusted to 2.3 by the addition of 25 percent aqueous formic acid. An amount (86.0 parts) of crotonylidenediurea is added to the reaction vessel and the system is heated to reflux temperature (about C) and azeotropic distillation of water from the reaction mixture is continued until the temperature of the resin system reaches 117 C. The system is then cooled to ambient temperature and the product butylated methylolated crotonylidenediurea adjusted to a solids content of 50 percent by the addition of butanol.

EXAMPLE Vll Preparation of Benzyloxymethylated Crotonylidenediurea Example V is repeated in every essential respect with the exception that methyl Formcel is replaced by a mixture of 405 parts of 37 percent formalin (uninhibited) and 688 parts of benzyl alcohol. The system is likewise heated to atmospheric reflux temperature for 1 hour and then cooled to approximately 55 C by the addition of another 500 parts of benzyl alcohol. Subsequent to this step Example V is followed in every essential detail and benzylated methylolated crotonylidenediurea thus produced.

EXAMPLE VlII Preparation of Butoxymethylated Crotonylidenediurea Crotonylidenediurea (344.0 grams), 92 percent flake paraformaldehyde (196.0 grams, containing grams of formaldehyde and 16 grams of water), n-butanol (518.0 grams), and 10 percent aqueous sodium carbonate solution (30 grams) are charged to a reaction vessel equipped with a phase separation head. The mixture is heated to reflux (about 101103 C) and held thereat for 75 minutes. The pH at the end of this reflux period is 7.2. Aqueous formic acid, 88 percent (5.0 grams), is then added to lower the pH to 5.3, and water is removed from the reaction mixture by azeotropic distillation until the temperature of the resin system reaches 1 17 C. After cooling to ambient temperature, the reaction mixture is filtered to give a clear solution of the product, butylated methylolated crotonylidenediurea.

EXAMPLE 1X Preparation of Methoxymethylated Crotonylidendiurea Crotonylidenediurea (344.0 grams), 92 percent flake paraformaldehyde (329.8 grams, containing 303.4

grams of formaldehyde and 26.4 grams of water), water (34.3 grams), and methanol (287.5 grams) are charged to a reactor and heated to reflux (about 94 C). After refluxing for 45 minutes, the pH is 5.4. Aqueous formic acid, 88 percent is added to lower the pH to 3.1. Refluxing is continued for an additional 20 minutes, then the mixture is cooled to 55 C and additional methanol (416.5 grams) is added. The mixture is maintained at 55 C for 4 hours, cooled to ambient temperature, and filtered to give a clear solution of the product, methylated methylolated crotonylidenediurea.

EXAMPLE X Preparation of Methylolated 2,7-Dioxo-4,5-dimethyldecahydropyrimido-[4,5-d]-pyrimidine To a suitable reaction vessel equipped with conventional agitation means are charged 239 grams (2.94 moles) of 37 percent formalin (uninhibited") and 15 grams of a 10 percent aqueous solution of sodium carbonate. To the resulting mixture is added, with agitation, 198 grams (1.0 mole) of crystalline 2,7-dioxo-4,5- dimethyl-decahydropyzimido-[4,5-d]-pyrimidine. The reaction mixture is then cooled to ambient temperature, the pH is adjusted to 7.0, and the reaction mixture filtered to remove insolubles. The clear filtrate contains 2.5 percent free formaldehyde as determined by the sodium sulfite method described in Walker, Formaldehyde, 3d ed., p. 486 (Reinhold, NY. 1964). The concentration of aminoplast material in the aqueous filtrate is 60 percent by weight as determined gravimetrically, i.e., by evaporating an aliquot sample of the solution at 70 C for 6 hours and weighting the residue. The product, of course, is aminoplast material (B).

EXAMPLE Xl This example illustrates a variant of the procedure used in Example X to produce the methylolated material (B).

To a suitable reaction vessel equipped with conventional agitation means are charged 2,919 grams (36 moles) of 37 percent formalin (uninhibited) and 135 grams of a 10 percent aqueous solution of sodium carbonate. To the resulting mixture is added, with agitation, 1,982 grams (9 moles) of crystalline 2,7-dioxo- 4,5-dimethyl-decahydropyrimido-[4,5-d]-pyrimidine. The reaction mixture, having a pH of between about 9 and about 9.5, is then heated at reflux temperature for minutes and cooled to 55 C. An additional charge of 135 grams of 10 percent aqueous sodium carbonate and 990 grams (5 moles) 2,7-dioxo4,5-dimethyldecahydropyrimidio-[4,5-d]-pyrimidine are added and the reaction mixture is again heated to reflux temperature and maintained thereat for 30 minutes. Upon recooling the reaction mixture to ambient temperature, neutralizing the pH, and filtering, a solution of methylolated 2,7-dioxo-4,5-dimethyl-decahydropyrimido- [4,5-d]-pyrimidine is obtained which contains 2.0 percent unreacted formaldehyde.

EXAMPLE X11 Reacted formaldehyde pyrimido-[4,5-d]-Pyrimidine The clear filtrate of Example X is charged to a reaction vessel equipped with a phase separation head, and the pH is adjusted to a value of 3.0 by the addition of 25 percent aqueous formic acid. An amount (370 parts) of butanol is added to the reaction vessel and the system is heated to reflux temperature (about 100 C) and azeotropic distillation of water from the reaction mixture is continued until the temperature of the resin system reaches 117 C. The system is then cooled to ambient temperature and the product, butoxymethylated 2,7-dioxo-4,5-dimethyl-decahydropyrimido- [4,5-dl-pyrimidine is adjusted to a solids content of 50 percent.

EXAMPLE Xlll Preparation of Cyclohexyloxymethylated 2,7-Dioxo- 4,5-Dimethyl-Decahydropyrimido-[4,5-d]-Pyrimidine The clear filtrate of Example X1, above, is charged to a reaction vessel equipped with a phase separation head, and the pH is adjusted to a value of 3.0 by the addition of 25 percent aqueous formic acid. An amount (5,000 grams; 50 moles) of cyclohexanol is added to the reaction vessel and the system heated to reflux temperature and azeotropic distillation of water from the reaction mixture is continued until the temperature reaches about C. To guard against product resin decomposition or polymerization, azeotropic distillation during the final stages is carried out under vacuum. The system is then cooled to ambient temperature and the product, cyclohexyloxymethylated 2,7-dioxo-4,5- dimethyl-decahydropyrimido-[4,5-d]-pyrimidine adjusted to the desired solids content.

EXAMPLE XlV Preparation of Methoxymethylated 2,7-Dioxo-4,5- Dimethyl-Decahydropyrimido-[4,5-d]-Pyrimidine This example illustrates a variant of the procedure used in Examples X11 and X111 to produce an alkylated (i.e., methylated) methylolated 2,7-dioxo-4,5- dimethyl-decahydropyrimido-[4,5-d]-pyrimidine.

An amount (272.0 parts) of 55 percent methyl Formcel containing 149.6 parts of formaldehyde (55 percent by weight), 95.2 parts of methanol (35 percent by weight) and 10 percent water is charged to a reaction vessel, and the pH is adjusted to a value of 3.0 by the addition of an appropriate amount of 25 percent aqueous formic acid. To the reaction vessel is then added 198.0 parts of 2,7-dioxo-4,5-dimethyldecahydropyrimido-[4,5-d]-pyrimidine. The system is heated to reflux temperature (about 96) and maintained thereat for approximately 1 hour. At the end of this period, the temperature of the reaction mixture is reduced to approximately 55 C., followed by the addition of 262.0 parts of methanol. This temperature is maintained for a period of about 2 hours, during which time the pH is kept constant at 3.0 by the addition of appropriate quantities of 25 percent formic acid. At the end of the 2-hour holding period, the reaction system is cooled to ambient temperature and the pH adjusted to 7.8 with 10 N sodium hydroxide. The reaction mixture is then filtered and evaporated under reduced pressure to remove water and excess methanol. The resulting residue of methoxymethylated 2,7-dioxo-4,5- dimethyl-decahydropyrimido-[4,5-d]-pyrimidine is redissolved in sufficient isopropanol to produce a solution containing 50 percent solids.

EXAMPLE XV Preparation of Butoxymethylated 2,7-dioxo-4,5- Dimethyl-Decahydropyrimido-[4,5-d]-Pyrimidine Butyl Formcel (206.0 parts) containing 82.4 parts of formaldehyde (40 percent by weight) and 109.2 parts of butanol (53 percent by weight) and n-butanol (62.0

parts) are charged to a reaction vessel equipped with a phase separation head, and the pH is adjusted to 2.3 by the addition of 25 percent aqueous formic acid. An amount (99.0 parts) of 2,7-dioxo-4,5-dimethy1- decahydropyrimido-[4,5-d]-pyrimidine is added to the reaction vessel and the system is heated to reflux temperature (about 100 C) and azeotropic distillation of water from the reaction mixture is continued until the temperature of the resin system reaches 117 C. The system is then cooled to ambient temperature and the product butoxymethylated 2,7-dioxo-4,5-dimethyldecahydropyrimido-[4,5-d]-pyrimidine adjusted to a solids content of 50 percent by the addition of butanol.

EXAMPLE XVI Preparation of Benzyloxymethylated 2,7-Dioxo-4,5- Dimethyl-Decahydropyrimido-[4,5-d]-Pyrimidine Example XIV is repeated in every essential respect with the exception that methyl Formcel is replaced by a mixture of 405 parts of 37 percent formalin (uninhibited) and 688 parts of benzyl alcohol. The system is likewise heated to atmospheric reflux temperature for one hour and then cooled to approximately 55 C. by the addition of another 500 parts of benzyl alcohol. Subsequent to this step Example V is followed in every essential detail; benzyloxymethylated 2,7-dioxo-4,5- dimethyl-dedahydropyrimido-[4,5-d]-pyrimidine is thus produced.

EXAMPLE XVII Decahydropyrimido-[4,5-d]-Pyrimidine A quantity (396.0 grams) of 2,7-dioxo-4,5-dimethyldecahydropyrimido-[4,5-d]-pyrimidine, 92 percent flake paraformaldehyde (196.0 grams; contains 180 grams of formaldehyde and 16 grams of water), nbutanol (518.0 grams) and percent aqueous sodium carbonate solution (30 grams) are charged to a reaction vessel equipped with a phase separation head. The mixture is heated to reflux (about 101103 C) and held thereat for 75 minutes. The pH at the end of this reflux period is 7.2. Aqueous (88 percent) formic acid (5.0 grams), is then added to lower the pH to 5.3, and water is removed from the reaction mixture by azeotropic distillation until the temperature of the resin system reaches 1 17 C. After cooling to ambient temperature, the reaction mixture is filtered to give a clear solution of the product, butoxymethylated 2,7-dioxo-3,4- dimethyl-decahydropyrimido-[4,5-d]pyrimidine.

EXAMPLE XVIII Preparation of Methoxymethylated 2,7-dioxo-4,5- Dimethyl-Decahydropyrimido-[4,5-d1-Pyrimidine A quantity (396.0 grams) of 2,7-dioxo-4,5-dimethy1- decahydropyrimido-[4,5-d]-pyrimidine, 92 percent flake paraformaldehyde (329.8 grams; contains 303.4 grams of formaldehyde plus 26.4 grams of water), and

V methanol (287.5 grams) are charged to a reactor and;

minutes the pH is 5.4. Aqueous formic acid (88 percent) is added to lower the pH to 3.1. Refluxing is continued for an additional 20 minutes, the mixture is cooled to 55 C., and additional methanol (416.5 grams) is added. The mixture is maintained at 55 C. for 4 hours, cooled to ambient temperature, and filtered to give a clear solution of the product methoxymethylated 2,7-dioxo-3,4-dimethy1- decahydropyrimido-[4,5-d]-pyrimidine.

EXAMPLE XIX Panels, Aluminum 3003-H14, Bonderite 721 treatment, 4 inches x 8 inches (for flexibility tests). Purchased from Hooker Chemical Co., Parker Division, Detroit, Michigan. Paint films are obtained by spraying. The wet films are allowed to air dry for about 10 to 15 .minutes, and then oven cured at specified temperatures for specified times. Rate of cure is determined by plotting development of hardness (pencil test) vs. cure temperature and time. Gloss: Standard gloss angle measurement determined on a Hunterlab Model D16 jGlossmeter (Hunter Associates Laboratories, Inc.,

Fairfax, Va.) in accordance with ASTM D523.

The etherified methylolated crotonylidenediurea products of Examples V and VI, above, and the etherified methylolated 2,7-dioxo-4,5-dimethyldecahydropyrimido products of Examples XIV and XV, above, are formulated into baking enamels (alkyd- '/amine ratios of 90/10, 80/20 and /30) according to the conventional method and formulation shown in the following table I.

TABLE I WHITE BAKING ENAMEL Roller Mill Grind Pounds Pounds Pounds Titanium Dioxide 16.6 16.6 16.6 Duraplex ND-77B (60% Solids) 11.7 11.7 11.7 Mix With Duraplex ND-77B (60% Solids) 13.3 10.5 7.8 Amino Resin (50% Solids) 3.4 6.7 10.0 Xylol 8.6 8.1 7.5 Catalyst Solution 0.6 0.5 0.5 Mimi.

Percent Solids 62.1 62.1 62.1 Pigment/Vehicle 1/1 1/1 1/1 Alkyd/Amino 90/10 80/20 70/30 Catalyst is 20% solution of amyl acid phosphate in methanol Test panels prepared from these formulations exhibited the properties shown in Table 11, below:

TABLE II PROPERTIES OF ENAMEL PANELS (Oven Time 30 Minutes) Cone. Pencil Reverse Conical 1% Tide* 5% NaOH Merthiolate Aminoplast: Temp. (by weight) Hardness Impact Mandrel 50 Hours 5-24 1-24 (inchlbs) /10 4 4-6 0 2-0 **SS METHYLATED 250F 80/20 6 2-4 0.38 0 2-2 SS AMINQPLAST 70/30 6 2-4 0.88 0 2-2 S-S PREPARED IN 90/10 4 6-8 0 2-0 SS EXAMPLE V 300F /20 6 2-4 0.13 0 2-2 SS Tide is a trademark for a detergent sold by Proctor 8; Gamble, Cincinnati, Ohio.

"S Stain "'NS No stain (1) Recorded after 5 hours and after 24 hours (2) Recorded after 1 hour and after 24 hours.

As is evident from Table 1, above, the novel curing process of the present invention provides coatings which exhibit very desirable physical properties and chemical resistance. All test panels had commerically acceptable gloss.

The tests for physical and chemical properties reported in table 1, above, are conventional.

Conical Mandrel ASTM D 522 Reverse lmpact (Gardner Laboratories, Bethesda, Md.) Pencil Hardness 3B, 28, B, HE, P. H, 2H, 3H, 4H (inincreasing hardness) Tide/50 hr. ASTM D 2248 Stain and Chemical Resistance Tests ASTM D 1308 While the tests carried out hereinabove use alkydlamino resin weight concentrations of 90/ 10, 80/20 and 70/30, based on the total weight of the alkyd and aminoplast components, these are merely illustrative. lf desired, concentrations in the range of about 95/5 to about 40/60 may be used in preparing various coating TABLE ll PROPERTIES OF ENAMEL PANELS (Oven Time 30 Minutes) Conc. Pencil Reverse Conical 1% Tide 5% NaOH Merthiolate Aminoplast: Temp. (by weight) Hardness lmpact Mandrel 50 Hours 5-24 1-24 (inch-lbs) 90/10 4 8-10 2-0 S-S BUTYLATED 250F 80/20 7 2-4 1.0 0 8-0 "*NS-NS AMINOPLAST 130. 7 2-4 1 2s 0 10-4 NSS PREPARED 90/10 4 6-8 0 2-0 S-S EXAMPLE Vl 300F 80/20 6 2-4 0.6 0 8-2 NSS HB-F 4 7 7 2-4 1.88 0 10-2 NSS F-H 90/10 4 4-6 0 2-0 S-S 2H-3H 7 METHYLATED 250F 80/20 6 2-4 0.38 0 2-2 S-S 3H-4H 8 AMINOPLAST 70/30 6 2-4 0.88 0 2-2 S-S PREPARED 1N 90/10 4 6-8 0 2-0 S-S EXAMPLE XIV 300F 80/20 6 2-4 0.13 0 2-2 S-S 90/10 4 8-10 0 2-0 S-S Butvlated 250P 80/20 7 2-4 1.0 0 8-0 NSNS AhflIflOPLAST 70110 7 2-4 1.25 0 10-4 NSS PREPARED IN 90110 4 6-8 0 2-0 S-S EXAMPLE XV 300F 80/20 6 2-4 0.63 0 8-2 NSS 70/30 7 2-4 1.88 0 10-2 NSS Conc. Ethanol Acetone 19% HCl 49% H 80. 100% HOAc Aminoplast: Temp. (by weight) 1-24 1-24 l-24 1-24 m 1-24 90/ 10 2-0 2-2 2-0 2-2 6-0 METHYLATED 250F 80/20 2-2 6-6 2-0 2-2 10-0 AMINOPLAST 8-8 2-2 2-0 4-2 0-0 Chemical Tests PREPAREDTN 90/10 2-2 2-0 2-0 4-2 6-0 0 denuded EXAMPLE V 300F 80/20 2-2 2-0 2-0 4-2 6-0 10 unaffected 90/10 8-2 0-0 2-0 8-2 2-0 BUTYLATED 250P /20 8-8 0-0 2-0 10-2 10-6 AIMQEL L 7.0139 25-8 6-6 2-0 2 2 0-0 PREPARED lN /10 2-2 0-0 2-0 4-2 0-0 EXAMPLE Vl 300F 80/20 4-2 6-0 2-0 4-2 6-0 90/ 10 2-0 2-2 2-0 2-2 6-0 METHYLATED 250F 80/20 2-2 6-6 2-0 2-2 10-0 AMINOPLAST m 84; 2-2 2-0 4-2 o-o PREP/REE lN 90/10 2-2 2-0 2-0 4-2 6-0 EXAMPLE XIV 300F 80/20 2-2 2-0 2-0 2-2 6-0 90/10 8-2 0-0 2-0 8-2 2-0 BUTYLATED 250F 80/20 8-8 0-0 2-0 10-2 10-6 AMINOPLAST 13 84; 6-6 2-o 2-2 0-0 PREPARED [N 90/ 10 2-2 0-0 2-0 4-2 0-0 EXAMPLE XV 300F 80/20 4-2 6-0 2-0 2-2 6-0 compositions, depending upon the end use intended for 50 these compositions. Generally, a concentration in the range of about 93/7 to about 55/45 is preferred.

EXAMPLE XX The butoxymethylated crotonylidenediurea product 55 of Example Vl, above, is used to prepare various white baked enamels according to the procedure in Example XIX using different curing catalysts. The following Table III illustrates the results with respect to whiteness e rfibs bak P BF butyl acid phosphate amyl acid phosphate very slight yellow no discoloration amyl acid phosphate having the formula:

wherein R is a hydrogen substituent or an n-amyl substituent and at least one of said R substituents is n-amyl.

2. The improved process according to claim 1 wherein the alkyd resin coating composition component is present in a concentration of between about 40 and about percent by weight based on the total weight of alkyd resin and aminoplast, and the amyl acid phosphate is present in amounts of between about 0.05 and about 2 percent by weight based on the total weight of the baked enamel coating composition.

3. The improved process according to claim 2 wherein the alkyd resin coating composition component is present in the concentration of between about 55 and about 93 percent by weight, and the amyl acid phosphate is present in amounts of between about 0.1 and about 1 percent by weight.

4. The improved process according to claim 1 wherein said curing is conducted in the presence of at least about 0.1 percent by weight of urea based on the total weight of the enamel coating composition.

5. The improved process according to claim 4 .wherein said curing is conducted in the presence of be tween about 0.2 and about 0.7 percent by weight of urea.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,808,039 Dated April 30, 1974 Inventor(s) Edward J. Kuzma It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 7, line 62, delete--"Rea cted formaldehyde pyrimido- 4,5-q] -Pyrimidine"-and insert--"Prparati0n of Butoxymethylated 2 7-dioxo- -4,5-Dirhathyl-Decahyropyrimido- [4,5-dJ-Pyrimidine'f.

Column 11, in 61. v i s t "l%"- -befOre- 'f'1ide/5Q hr.-ASTM D Signed and sealed this 1st day .of October 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. I C. MARSHALL DANN Attesting Offifice x' Commissioner of Patents FORM PO-1OSD (10-69) uscoMM-Dc 60376-P69 11.5. GOVERNMENT PRINTING OFFICE: 1969 O-366334 

2. The improved process according to claim 1 wherein the alkyd resin coating composition component is present in a concentration of between about 40 and about 95 percent by weight based on the total weight of alkyd resin and aminoplast, and the amyl acid phosphate is present in amounts of between about 0.05 and about 2 percent by weight based on the total weight of the baked enamel coating composition.
 3. The improved process according to claim 2 wherein the alkyd resin coating composition component is present in the concentration of between about 55 and about 93 percent by weight, and the amyl acid phosphate is present in amounts of between about 0.1 and about 1 percent by weight.
 4. The improved process according to claim 1 wherein said curing is conducted in the presence of at least about 0.1 percent by weight of urea based on the total weight of the enamel coating composition.
 5. The improved process according to claim 4 wherein said curing is conducted in the presence of between about 0.2 and about 0.7 percent by weight of urea. 